Conjugated nanohoops provide a platform to study structure–property relationships; they are attractive hosts for supramolecular chemistry as well as promising candidates as new organic materials. We herein present [n]­cyclodibenzo­pentalenes ([n]­CDBPs) as antiaromatic analogues of [n]­cycloparaphenylenes. Platinum-mediated macrocyclization of dibenzopentalene boronic esters provided the trimer and tetramer with strain energies of up to 80 kcal mol–1. In the solid state, the cylindrical [4]­CDBP molecules align to form columnar structures. The larger hoop [4]­CDBP binds both fullerenes C60 and C70 with temperature-dependent exchange behavior, providing higher activation energies for the exchange compared to [10]­CPP. The antiaromatic character of the [n]­CDBPs paired with the cyclic conjugation leads to high HOMO energies and lowered LUMO energies with band gaps below 2 eV. This work presents a new class of the antiaromatic and nonalternant curved nanocarbons with intriguing supramolecular and ambipolar optoelectronic properties.